CN1564355A - Polymer loaded catalyst electrode in fuel cell and its prepn. method - Google Patents
Polymer loaded catalyst electrode in fuel cell and its prepn. method Download PDFInfo
- Publication number
- CN1564355A CN1564355A CNA2004100307660A CN200410030766A CN1564355A CN 1564355 A CN1564355 A CN 1564355A CN A2004100307660 A CNA2004100307660 A CN A2004100307660A CN 200410030766 A CN200410030766 A CN 200410030766A CN 1564355 A CN1564355 A CN 1564355A
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- China
- Prior art keywords
- electrode
- catalyst
- polyaniline
- supporting layer
- fuel cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Disclosed pole is composed of support layer, conducting macromolecule polyaniline and catalyst Pt or Pt-Ru alloy. Macromolecule polyaniline, which possesses dual electron and proton conduction and high stability, instead of traditional carbon material is as carrier for dispersing catalyst Pt. Carrying out activating treatment for support layer of pole, and using electrochemical method polymerizes polyaniline on the support layer of pole. Using electrodeposit method deposits Pt or Pt/Ru to polyaniline. Features of the invention are: raising degree of dispersion of catalyst, enlarging area of catalyst, transferring H+ to electrolyte to raise use ratio of Pt; quick preparing procedure, easy of implementation and good repeatability.
Description
Technical field
The present invention relates to catalytic electrode material and preparation thereof in the fuel cell.
Background technology
It is few that fuel cell has energy loss, the low pollution, and energy density height, low noise advantages are considered to following electric powered motor and the most promising chemical power source of other civilian occasion.At present, the preparation key technology of fuel cell is ripe, but the electrode of fuel cell adopts Pt as catalyst more, because Pt is a noble metal, resource-constrained costs an arm and a leg, so the biggest obstacle that fuel cell is used is that cost of manufacture is too high.In order to reduce cost, reduce the consumption of Pt, the method that generally adopts is in the preparation process of electrode now, selection has the material of high-specific surface area such as graphite, active carbon etc. as carrier, supported catalyst Pt is compound to be the Pt/C catalyst, improve the decentralization of catalyst Pt, promptly reduce the consumption of Pt, improve the utilance of Pt.But traditional carbon carrier can only electron conduction, can not proton conductive, and the catalyst Pt that exists the carrier inside load can not directly contact with the dielectric film in the fuel cell, thereby hinders H
+Transmission, cause the reduction of catalyst utilization.
Fuel cell electrode is divided into two-layer.One deck is a supporting layer, plays the effect of support catalyst, collected current and conductive liquid and product.Another layer is a catalyst layer, and it is by eelctro-catalyst, carrier and the preparation of waterproofing agent polytetrafluoroethylene.Since fuel cell adopts be solid-state proton exchange membrane as electrolyte, can't as liquid electrolyte, infiltrate the electrode micropore, and the H in the electrode reaction
+Must electrode reaction be proceeded, even therefore adopt the Pt/C catalyst, the utilance of Pt be still very low in the electrode.Consider to increase effective catalyst surface area for this reason, to reduce the Pt carrying capacity, reduce contact resistance, document Mikhaylova A A, Khazova O A and Bagotzky V S.Electrocatalytic andadsorption properties of platinum microparticles electrodeposited onto glassy carbonand into Nafion films.J Electroanal Chem, 480 (2000) 225 and Thompson S D, JordanL R, Shukla A K and Forsyth M.Platinum electrodeposition from H
3Pt (SO
3) reported among the OHsolutions.J Electroanal Chem.515 (2001) 61 direct with proton exchange polymer Nafion solution impregnation Pt/C porous gas diffusive electrode, and then be hot-pressed onto the preparation method who forms electrode on the proton exchange membrane, improve the utilance of electrode Pt.This method has increased the utilance of Pt effectively, but its shortcoming is: spray into or the Nafion solution that immerses is difficult to usually infiltrate fully in the Catalytic Layer and with catalyst granules and fully contacts, thereby also influenced H
+Abundant transmission.
Summary of the invention
The present invention is directed to the carrier carbon utilized in the fuel cell electrode preparation can only electron conduction, the problem that carrier inside catalyst Pt utilance is low, propose this electrode by supporting layer and the conductive polymer polyanilinc and catalyst Pt or the Pt-Ru alloy composition that cover on the supporting layer, utilize the polymer polyanilinc that has electronics and dual electric conductivity of proton and high stability simultaneously to replace the carrier of traditional carbon body material as dispersed catalyst Pt.Carry out activation processing by supporting layer to electrode, utilize electrochemical method electropolymerization polyaniline on the supporting layer of electrode, and with the method for electro-deposition, Pt or Pt/Ru are deposited in the polyaniline, form the electrode catalyst of fuel cell layer that conductive polymer polyanilinc is done carrier.The catalyst electrode of this method preparation promptly can improve the decentralization of catalyst Pt, makes long-pending increase of effective catalytic surface of electrode, can make the H of carrier inside catalytic reaction again
+Be delivered to dielectric film, thereby improve the utilance of Pt.
The fuel cell polymer supported catalyst electrode of the present invention's preparation comprises two-layer, one deck is a supporting layer, by a kind of composition the in carbon paper, carbon cloth, the metal foam, another layer is a catalyst layer above the supporting layer, is made up of eelctro-catalyst Pt or Pt-Ru alloy, carrier polyaniline and waterproofing agent polytetrafluoroethylene.
Preparation process of the present invention:
1, the preliminary treatment of supporting layer
Place 5-30%NaOH or KOH solution to boil 5-30 minute supporting layer, extremely neutral with distilled water flushing, then at 10-30%HNO
3Boiled in the solution 10-20 minute, extremely neutral with distilled water flushing.
2, the electropolymerization of aniline
Electrolytic cell is put into as electrode in the treated clean back of supporting layer, adds aniline and the H that second distillation is crossed in the electrolytic cell
2SO
4Be mixed with 0.01-0.5molL
-1Aniline adds 0.2-1.0 molL
-1H
2SO
4Solution.Utilize the method for cyclic voltammetric, constant potential or pulse potential, the control potential range is between-0.1-1.3V (with respect to calomel electrode), and control polymerization electric weight scope is at 0.2-0.8mC/cm
2Between, powering at supporting layer polymerize polyaniline.
3, the electro-deposition of catalyst Pt or Pt-Ru
To place 1-20mmolL with the supporting layer of polyaniline
-1H
2PtCl
6+ 0.5mol L
-1H
2SO
4Or adding 1-20mmol L
-1RuCl
3Electrolyte in, utilize cyclic voltammetric method electro-deposition catalyst, the CONTROLLED POTENTIAL sweep limits is-0.2～0.55V (with respect to a calomel electrode), control deposition electric weight scope is at 0.01-0.03mC/cm
2Between.
4, the preparation polyaniline carries Pt or Pt-Ru electrode.
After deposition Pt or the Pt-Ru, electrode was immersed in polytetrafluoroethylene (PTEF) solution of 2%-5% 2-10 minute, dry under 60 ℃-140 ℃ temperature, make polyaniline and carry Pt or Pt-Ru electrode.
The electrode that the present invention is prepared, polyaniline deposits on the supporting layer as the carrier of catalyst, and be assembled into electrode, because the long-chain conjugated structure and the reversible doping of proton on the polyaniline molecule long-chain of polyaniline molecule itself make polyaniline have the performance of electronics and the dual conduction of proton simultaneously.Fuel cell is in when work, and polyaniline carries the continuous passage that the Pt electrode not only exists reacting gas and water, and the catalyst of polyaniline and load itself also possesses proton, two kinds of channel functions of electronics, makes that the reaction three-dimensional in the fuel cell electrode is carried out.Having overcome the conventional carbon carrier can only electron conduction, the shortcoming that the carrier inside catalyst Pt can not directly be contacted with membrane electrode.Therefore, conductive polymer polyanilinc can replace conventional graphite to be used as catalyst carrier in fuel cell electrode, improves the utilance of catalyst Pt, has optimized electrode structure.After the polyaniline polymerization, catalyst particles makes long-pending increase of effective catalytic surface of electrode in the high degree of dispersion of electrode surface, also can improve catalyst utilization.Electrode production process is rapid simultaneously, and technology is simple and easy to do, need not special installation, favorable reproducibility.In addition, polyaniline loaded Pt catalyst electrode not only can be used for fuel cell electrode, can also be used for other battery, and the processing of polluting, many fields such as material protection.
Embodiment
Below in conjunction with embodiment, further specify this explanation.
1, the preliminary treatment of supporting layer carbon paper
The supporting layer of choosing is a carbon paper, places 10%NaOH solution to boil 20 minutes electrode supporting layer carbon paper, and is extremely neutral with distilled water flushing, then at 10%HNO
3Boiled in the solution 20 minutes, extremely neutral with distilled water flushing.
2, the electropolymerization of aniline
Carbon paper electrode is treated puts into electrolytic cell after cleaning, and puts in the electrolytic cell 0.2mol L is housed
-1Aniline adds 0.5 mol L
-1H
2SO
4In the electrolytic cell of solution.Utilize the electrochemical method of cyclic voltammetric, the gated sweep potential range between-0.2V-1.0V (with respect to calomel electrode), cycle-index 11, sweep speed per second 50mV.Power at carbon paper and to polymerize polyaniline.
3, the electro-deposition of catalyst Pt
The carbon paper that is modified with polyaniline is placed 5mmol L
-1H
2PtCl
6+ 0.5mol L
-1H
2SO
4In the electrolyte, utilize cyclic voltammetric method electro-deposition Pt, the electric potential scanning scope is-0.2～0.55V (with respect to a calomel electrode), sweeps speed and is 50mVs
-1, scanning times 20-50 time.
4, the preparation polyaniline carries the Pt electrode
After the deposition Pt, electrode is utilized redistilled water flushing, immersed then in 5% polytetrafluoroethylene (PTEF) solution 2 minutes, under 80 ℃ temperature dry 5 minutes, take out and naturally cool to room temperature, just make polyaniline and carry the Pt electrode.
Because the present invention has improved the decentralization of catalyst Pt, make the H of carrier inside catalytic reaction
+Be delivered to dielectric film, thereby the utilance of Pt 7.6 times have been improved than C carried catalyst.
Claims (3)
1, polymer supported catalyst electrode in a kind of fuel cell, form by supporting layer and catalyst layer, it is characterized in that: supporting layer is by a kind of composition the in carbon paper, carbon cloth, the metal foam, and the catalyst layer above the supporting layer is made up of eelctro-catalyst Pt or Pt-Ru alloy, carrier polyaniline and waterproofing agent polytetrafluoroethylene.
2, the preparation method of polymer supported catalyst electrode in the fuel cell is characterized in that: mainly comprise the steps:
A) electropolymerization of aniline
Pretreated supporting layer is put into electrolytic cell as electrode, adds aniline and the H that second distillation is crossed in the electrolytic cell
2SO
4Be mixed with 0.01-0.5molL
-1Aniline adds 0.2-1.0molL
-1H
2SO
4Solution.Utilize the method for cyclic voltammetric, constant potential or pulse potential, the control potential range is between-0.1-1.3V (with respect to calomel electrode), and control polymerization electric weight scope is at 0.2-0.8mC/cm
2Between, powering at supporting layer polymerize polyaniline;
B) electro-deposition of catalyst Pt or Pt-Ru
To place 1-20mmolL with the supporting layer of polyaniline
-1H
2PtCl
6+ 0.5molL
-1H
2SO
4Or adding 1-20mmolL
-1RuCl
3In the electrolyte, utilize cyclic voltammetric method electro-deposition Pt, the CONTROLLED POTENTIAL sweep limits is-0.2～0.55V (with respect to a calomel electrode), and control deposition electric weight scope is at 0.01-0.03mC/cm
2Between;
C) the preparation polyaniline carries Pt or Pt-Ru electrode
After the deposition, electrode was immersed in polytetrafluoroethylene (PTEF) solution of 2%-5% 2-10 minute, dry under 60 ℃-140 ℃ temperature, make polyaniline and carry Pt or Pt-Ru electrode.
3, method as claimed in claim 2, it is characterized in that: the preliminary treatment of supporting layer is to place 5-30%NaOH or KOH solution to boil 5-30 minute supporting layer,, in 10-30%HNO3 solution, boiled 10-20 minute then to neutral with distilled water flushing, extremely neutral with distilled water flushing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100307660A CN1243389C (en) | 2004-04-02 | 2004-04-02 | Polymer loaded catalyst electrode in fuel cell and its prepn. method |
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|---|---|---|---|
| CNB2004100307660A CN1243389C (en) | 2004-04-02 | 2004-04-02 | Polymer loaded catalyst electrode in fuel cell and its prepn. method |
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| Publication Number | Publication Date |
|---|---|
| CN1564355A true CN1564355A (en) | 2005-01-12 |
| CN1243389C CN1243389C (en) | 2006-02-22 |
Family
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007024619A1 (en) | 2007-05-24 | 2008-12-04 | Technische Universität Darmstadt | A process for the preparation of a supported catalyst for the oxidation of carbon monoxide, this supported catalyst and a process for the oxidation of carbon monoxide |
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN103094527A (en) * | 2013-01-12 | 2013-05-08 | 上海大学 | Method for reducing irreversible capacity loss of cathode material of lithium ion battery in initial charge |
| CN104737352A (en) * | 2012-10-22 | 2015-06-24 | 国立大学法人东京大学 | Cell |
| CN106898497A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | Bifunctional electrodes and its preparation method and application |
| CN106910641A (en) * | 2015-12-18 | 2017-06-30 | 中国科学院大连化学物理研究所 | A kind of bifunctional electrodes and its preparation method and application |
| CN108346809A (en) * | 2018-03-12 | 2018-07-31 | 常州大学 | A kind of preparation method of the porous polyaniline electrode materials of Pt-Ag/ |
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
| CN111146461A (en) * | 2019-12-31 | 2020-05-12 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN112993272A (en) * | 2021-03-26 | 2021-06-18 | 苏州弗尔赛能源科技股份有限公司 | Polymer composite diffusion layer for fuel cell, membrane electrode assembly and preparation method thereof |
| US20230227993A1 (en) * | 2022-01-18 | 2023-07-20 | Qingdao university of technology | Photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes, the preparation method thereof and a method of using the photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes |
-
2004
- 2004-04-02 CN CNB2004100307660A patent/CN1243389C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007024619A1 (en) | 2007-05-24 | 2008-12-04 | Technische Universität Darmstadt | A process for the preparation of a supported catalyst for the oxidation of carbon monoxide, this supported catalyst and a process for the oxidation of carbon monoxide |
| CN102592837A (en) * | 2012-03-12 | 2012-07-18 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN102592837B (en) * | 2012-03-12 | 2014-01-15 | 河北师范大学 | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor |
| CN104737352A (en) * | 2012-10-22 | 2015-06-24 | 国立大学法人东京大学 | Cell |
| CN104737352B (en) * | 2012-10-22 | 2017-05-24 | 国立大学法人东京大学 | Cell |
| US10566618B2 (en) | 2012-10-22 | 2020-02-18 | The University Of Tokyo | Cell |
| CN103094527A (en) * | 2013-01-12 | 2013-05-08 | 上海大学 | Method for reducing irreversible capacity loss of cathode material of lithium ion battery in initial charge |
| CN103094527B (en) * | 2013-01-12 | 2015-05-27 | 上海大学 | Method for reducing irreversible capacity loss of cathode material of lithium ion battery in initial charge |
| CN106910641A (en) * | 2015-12-18 | 2017-06-30 | 中国科学院大连化学物理研究所 | A kind of bifunctional electrodes and its preparation method and application |
| CN106898497A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | Bifunctional electrodes and its preparation method and application |
| CN108346809A (en) * | 2018-03-12 | 2018-07-31 | 常州大学 | A kind of preparation method of the porous polyaniline electrode materials of Pt-Ag/ |
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
| CN109293918B (en) * | 2018-09-05 | 2021-05-11 | 东华大学 | Polyaniline nano-cluster and preparation method and device thereof |
| CN111146461A (en) * | 2019-12-31 | 2020-05-12 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN111146461B (en) * | 2019-12-31 | 2021-06-04 | 中北大学 | Preparation method of paper-graphite-PANI-Pt electrode and application of paper-graphite-PANI-Pt electrode in H catalysis2O2Application in electroreduction reaction |
| CN112993272A (en) * | 2021-03-26 | 2021-06-18 | 苏州弗尔赛能源科技股份有限公司 | Polymer composite diffusion layer for fuel cell, membrane electrode assembly and preparation method thereof |
| CN112993272B (en) * | 2021-03-26 | 2022-08-02 | 苏州弗尔赛能源科技股份有限公司 | Polymer composite diffusion layer for fuel cell, membrane electrode assembly and preparation method thereof |
| US20230227993A1 (en) * | 2022-01-18 | 2023-07-20 | Qingdao university of technology | Photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes, the preparation method thereof and a method of using the photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes |
| US11761110B2 (en) * | 2022-01-18 | 2023-09-19 | Qingdao university of technology | Photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes, the preparation method thereof and a method of using the photoanode film for the photocathode protection and the durability improvement of a reinforcing bar in concretes |
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| Publication number | Publication date |
|---|---|
| CN1243389C (en) | 2006-02-22 |
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